Herein, a new method to synthesise epoxide-based sequence-controlled polymers via anionic ring-opening monomer addition, a form of anionic ring-opening polymerisation, is presented. This technique allows in combination with post-polymerisation modification (PPM) reactions for the successful preparation of modified mPEG-b-oligo(allyl glycidyl ether) featuring the incorporation of one repeating unit on average at a time. Due to the possible introduction of a vast variety of molecules to the polymeric system via PPM reactions, a multitude of advanced functional polymeric materials can be generated. This, in combination with the chain extension reactions, allows for the synthesis of well-controlled and programmable architectures with particular properties. The structure of the sequence-controlled polymer was confirmed via 1H NMR spectroscopy, size exclusion chromatography, attenuated total reflection Fourier-transform infrared spectroscopy, and differential scanning calorimetry.